CN115057965B - Preparation method of N-vinylpyrrolidone/1-vinylimidazole copolymer - Google Patents
Preparation method of N-vinylpyrrolidone/1-vinylimidazole copolymer Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 61
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 12
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 80
- 239000000375 suspending agent Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 39
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 2
- 239000002270 dispersing agent Substances 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 11
- 239000012429 reaction media Substances 0.000 abstract description 11
- 238000010558 suspension polymerization method Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 54
- 238000007334 copolymerization reaction Methods 0.000 description 38
- 239000003999 initiator Substances 0.000 description 25
- 239000007788 liquid Substances 0.000 description 22
- 150000003254 radicals Chemical class 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000012213 gelatinous substance Substances 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses a preparation method of an N-vinyl pyrrolidone/1-vinyl imidazole copolymer, relates to the technical field of PVP copolymer preparation, and adopts a suspension polymerization method by using water as a reaction medium for VP/VI copolymer polymerization. The method has the effects of improving the polymerization effect of the VP/VI copolymer and simplifying the preparation process.
Description
Technical Field
The application relates to the technical field of PVP copolymer preparation, in particular to a preparation method of an N-vinyl pyrrolidone/1-vinyl imidazole copolymer.
Background
Polyvinylpyrrolidone (PVP) is colorless or yellowish clear liquid, and is widely applied to industries such as pharmacy, cosmetics, paint, adhesive and the like; the copolymer of NVP and 1-Vinylimidazole (VI) (i.e., VP/VI copolymer) is a custom functional polymer in PVP series products.
In the VP/VI copolymer, pyrrolidone units can be complexed with other molecules or structures in the form of hydrogen bonds, and imidazole structures can be combined with organic substrates such as proteins, enzymes and dyes to form stable complexes, and can also form complexes with metal ions such as iron ions, copper ions, nickel ions and silver ions, and have higher selectivity; the VP/VI copolymer can be applied to various aspects such as photographic technology, dyeing anti-corrosion agents for textile fibers and plastic surfaces, and the like.
At present, organic solvents such as ethanol, isopropanol and the like are generally used as reaction media for preparing VP/VI copolymers. However, it was found that the copolymer easily forms a lamellar gel substance which precipitates from the solution during the polymerization, and there are problems such as a low polymerization degree, a low VI segment content in the copolymer, and the like, resulting in that the polymerization objective is not achieved.
Disclosure of Invention
In order to improve the polymerization effect of NVP and VI, adjust the polymerization degree of the copolymer and improve the PVI content in the copolymer, the application provides a preparation method of an N-vinylpyrrolidone/1-vinylimidazole copolymer, which can achieve the polymerization degree and VI content of polymerization.
The application adopts the following technical scheme:
a method for preparing an N-vinylpyrrolidone/1-vinylimidazole copolymer, which uses water as a reaction medium for the copolymerization reaction;
adding suspending agent with the weight of 0.05-0.5% of the water.
Preferably, the method specifically comprises the following steps:
s1, adding the suspending agent or a mixture of the suspending agent and the dispersing aid agent into the water, and adding the 1-vinylimidazole and the free radical initiator under vigorous stirring;
or, adding the suspending agent or the mixture of the suspending agent and the dispersing aid agent and the 1-vinylimidazole and the free radical initiator into the water, and stirring vigorously;
s2, heating to a reaction temperature, reacting for a period of time, dropwise adding the N-vinyl pyrrolidone, and continuing to react for a period of time to obtain a VP/VI copolymer solution;
alternatively, the solution is dried after further removal of water to obtain VP/VI copolymer powder.
By adopting the technical scheme, water is used as a reaction medium for the copolymerization of the NVP and the VI, 1-vinylimidazole is added into the water and the suspending agent (or the suspending agent and the dispersing aid agent) to form a suspension containing the VI, and the inventor finds that the reactivity ratio of the monomer NVP is far higher than that of the monomer VI in the experimental process, so that the VI monomer is polymerized for a period of time, and then the NVP is dropwise added into the suspension containing the VI for polymerization; when the 1-vinylimidazole is used as a reaction medium for suspension polymerization, polymerization difficulty is low, a sheet-shaped gel substance is not generated, polymerization speed is high, the polymerization degree of the polymer is limited by a solvent, then the NVP monomer is continuously added dropwise, the copolymerization effect of NVP and VI is good, and copolymers can be formed; and water is used as a medium for the polymerization reaction, and after the polymerization reaction is finished, the organic solvent is not required to be subjected to aftertreatment in the prior art, so that the preparation process of the VP/VI copolymer is simplified, the production cost is further reduced, and meanwhile, the environment-friendly type polymerization catalyst has higher environment-friendly performance, and the problem that a copolymerization product cannot be applied to the fields of foods, medicines, daily chemicals and the like due to the residue of the organic solvent is avoided.
Preferably, 0.001-0.01% of a dispersion aid agent by weight of the water is also added.
By adopting the technical scheme, the dispersion aid agent is coated on the surface of the liquid drop, so that the interfacial tension can be further reduced, the coalescence of the liquid drop can be prevented, the liquid drop is dispersed more finely, and the polymerization reaction rate is improved.
Preferably, the suspending agent is a water-soluble high molecular compound.
Preferably, the suspending agent is a copolymer of N-vinylpyrrolidone and 1-vinylimidazole.
Preferably, the weight percentage of the polyvinyl imidazole in the suspending agent is 5-30%.
By adopting the technical scheme, the suspending agent is added into the water, and the 1-vinyl imidazole is mixed with the water in tiny liquid drops through the suspending agent, so that the VI monomer is partially homo-polymerized firstly, and then the VI monomer and the NVP continue to carry out copolymerization reaction, and further the copolymerization effect of the NVP and the VI is improved.
The copolymer of N-vinyl pyrrolidone and 1-vinyl imidazole is used as a suspending agent, so that the effect of the suspending agent on liquid dispersion can be achieved, and the suspending agent and a final copolymerization product are very close in composition and structure, so that the processing work of removing the suspending agent is not needed after the reaction is finished, the preparation process can be simplified, the introduction of impurities is reduced, and the quality of the VP/VI copolymer is improved.
Preferably, the weight ratio of the N-vinyl pyrrolidone to the 1-vinyl imidazole is 1 (0.01-0.5).
Preferably, the sum of the weight of the N-vinyl pyrrolidone and the weight of the 1-vinyl imidazole accounts for 5-40% of the total weight of the reaction raw materials.
By adopting the technical scheme, the reactivity ratio of the monomer NVP is far higher than VI, so that the NVP and VI input amount are controlled within a specific value range in the polymerization reaction process, and the effect of promoting the VP/VI copolymer to polymerize can be realized.
Preferably, the copolymerization employs an oil-soluble free radical initiator.
Preferably, the oil-soluble free radical initiator has a half-life of not more than 12 hours at 80 ℃.
By adopting the technical scheme, the free radical initiator is a substance generating free radical polymerization active center, which can influence the reaction rate of the polymer and the relative molecular mass of the polymer, and the azo free radical initiator is suitable for suspension polymerization and is used for polymerization of NVP and VI; when azo initiator such as AIBN, ABVN, AIBME is used as the initiator for VP/VI copolymer polymerization, the initiator is decomposed uniformly, the reaction temperature is proper, only one free radical is generated, no induction decomposition is caused, and the polymerization effect of NVP and VI is improved.
The principle of the invention is that in the prior art, organic solvents such as absolute ethyl alcohol, isopropanol and the like are adopted as reaction media for PVP and VI copolymerization reaction, but as the polymerization degree of the copolymer becomes larger or the copolymerization component in the copolymer changes, the compatibility of the copolymer and the organic solvents becomes poor, and the copolymer precipitates out of the reaction media when the established polymerization target is not reached, so that the polymerization fails. In order to solve the problems, the invention adopts water as a reaction medium, and because the solubility of the 1-vinyl imidazole in water is poor, the invention adopts a suspension polymerization method, so that the 1-vinyl imidazole forms small liquid drops and reacts for a period of time, then the NVP monomer with high polymerization rate is dripped into the suspension, the NVP has good water solubility and can form good copolymerization with VI, the NVP monomer with high polymerization rate is effectively prevented from self-polymerizing, and the copolymerization product also has certain water solubility or water dispersibility due to the good water solubility of PVP chain segments and can not form sediment, thereby achieving the copolymerization purpose.
The invention discovers that by adopting suspension polymerization, the free radical initiator initiates polymerization reaction in VI monomer droplets, then carries out copolymerization reaction with NVP monomer in water phase at a water-oil interface, and the water solubility of the copolymer is improved along with the progress of the copolymerization reaction, and the copolymerization reaction is gradually transferred into the water phase for carrying out. Therefore, the reaction conversion rate of the VI monomer is high, the residual monomer is few, the high conversion rate of the NVP monomer with high polymerization rate is realized, and the self-polymerization reaction of the NVP monomer is effectively avoided.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) In the application, water is used as a solvent system for copolymerizing NVP and VI, and the VI is firstly mixed with the water in the form of tiny liquid drops, so that the copolymerization of the NVP and the VI in the water is realized, the generation of flaky gelatinous substances is reduced, and the content of polyimidazole in the polymer is improved; meanwhile, after the polymerization reaction is finished, the organic solvent post-treatment step in the prior art is not needed, the preparation step of the VP/VI copolymer is simplified, the effect of saving the production cost is realized, the environment friendliness is high, and the product quality problem caused by organic solvent residues is avoided.
(2) The invention adopts the copolymer of N-vinyl pyrrolidone and 1-vinyl imidazole as suspending agent, the composition and structure of the suspending agent are very close to those of the copolymerization product, and the suspending agent can be well compatible and mixed with the copolymerization product, but not the impurities of the copolymerization product, so that the suspending agent impurities do not need to be removed further, and the suspending agent has strong competitive advantage in some application occasions with strict requirements on the impurity content, such as lithium ion batteries, biological medicines, foods and the like, because the removing work of a small amount of suspending agent impurities is not only large in workload, but also long in time and high in cost.
Detailed Description
The following more detailed description of the methods of preparation of the present application provides further details of the present application.
The present application provides a process for the preparation of an N-vinylpyrrolidone/1-vinylimidazole copolymer using water as a solution system for the polymerization of the N-vinylpyrrolidone/vinylimidazole copolymer.
In one embodiment, the preparation method specifically comprises the following steps:
s1, adding the suspending agent or a mixture of the suspending agent and a dispersion assisting agent into water, and adding the 1-vinylimidazole and a free radical initiator under vigorous stirring;
or, adding the suspending agent or the mixture of the suspending agent and the dispersing aid agent, the 1-vinylimidazole and the free radical initiator into the water, and stirring vigorously;
s2, heating to a reaction temperature, reacting for 0.5-3 hours, dropwise adding N-vinyl pyrrolidone, and continuing to react for a certain time to obtain VP/VI copolymer solution;
alternatively, the solution is dehydrated and dried to obtain VP/VI copolymer, which is a solid product.
In step 1 of the present application, the stirring speed is 300 to 1500rpm, and the stirring speed is related to the amount of the reaction monomer, the suspending agent and other materials to be added and the viscosity of the materials, so that the VI monomer in the aqueous phase is preferably uniformly dispersed and suspended into fine droplets. In the present invention, the stirring speed is related to the size and number of stirring blades and the size of the reaction vessel, and it is preferable that the VI monomer can be formed into droplets.
The reaction time before dropwise adding N-vinyl pyrrolidone in the step 2 can be adjusted according to the amount of 1-vinyl imidazole in the system, and when the amount of 1-vinyl imidazole monomer in the copolymerization reaction system is small, for example, 1-vinyl imidazole monomer accounts for 1-5% of the total reaction monomer weight, the reaction time at the moment can be 0.5-1 hour; when the amount of 1-vinylimidazole monomer in the copolymerization reaction system is large, for example, the 1-vinylimidazole monomer accounts for 25 to 30% by weight of the total reaction monomers, the reaction time may be longer, for example, 2 to 3 hours.
After the N-vinyl pyrrolidone is dropwise added in the step 2, the VI monomer is reacted for a period of time before the reaction, so that the reaction rate of the NVP monomer is higher, and the copolymerization reaction is finished after the reaction is continued for 1.5-5 hours; the reaction time can also be adjusted along with the total reaction monomer amount of the VI monomers and the NVP monomers or along with the NVP monomers, and the reaction time can be correspondingly increased if the amount of the monomers is more.
In one embodiment, the suspending agent is a water-soluble polymer compound, such as water-soluble polyvinyl alcohol, gelatin, hydroxypropyl methylcellulose, and the like. In a preferred embodiment, the suspending agent is a copolymer of N-vinylpyrrolidone and 1-vinylimidazole; more preferably, the weight percentage of the polyvinyl imidazole in the suspending agent is 5-30%, and specifically, the weight percentage of the polyvinyl imidazole is 5%, 10%, 15%, 18%, 20%, 25%, 30%, etc.
In the application, the N-vinyl pyrrolidone and 1-vinyl imidazole copolymer are used as suspending agents, new impurities are not introduced, the step of post-treatment of the VP/VI copolymer is reduced, the effect of simplifying the preparation process is achieved, and the product quality can be improved. In addition, when the suspending agent is a copolymer of N-vinyl pyrrolidone and 1-vinyl imidazole, the VI content of the suspending agent can be close to that of a copolymerization product as much as possible by selecting the suspending agent, namely the suspending agent can be better fused into the copolymerization product.
In the application, in step 1, a dispersing aid agent may be further added, specifically, the dispersing aid agent may be sodium dodecyl benzene sulfonate, hydroxypropyl methylcellulose, or other substances, so as to reduce the water-VI interface pressure, promote VI to disperse under stirring action to form stable droplets, and the dispersing aid agent may be adsorbed on the surface of the droplets to form an adsorption layer, so as to play a role in colloid protection on the droplets.
In one embodiment, the weight ratio of the N-vinylpyrrolidone to the vinylimidazole is 1: (0.01-0.5); the weight ratio of N-vinylpyrrolidone to the 1-vinylimidazole can be adjusted according to the K value and VI content of the desired copolymer; in a more preferred embodiment, the weight ratio of said N-vinylpyrrolidone to said vinylimidazole is 1: (0.1-0.4), specifically, the weight ratio may be 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, etc.
In one embodiment, the sum of the weight of the N-vinylpyrrolidone and the 1-vinylimidazole is 5-40% of the total reaction raw material weight, and specifically, the ratio may be 10%, 15%, 20%, 25%, 30%, etc.
In the application, the reactivity ratio of NVP is larger than that of 1-vinylimidazole, so that a free radical initiator is utilized to initiate polymerization reaction in VI monomer droplets, then NVP is added into a suspension containing polyvinylimidazole, the weight ratio of N-vinylpyrrolidone to 1-vinylimidazole and the ratio of the sum of the weights of N-vinylpyrrolidone and vinylimidazole in all reaction raw materials are further controlled, the tendency of copolymerization of NVP and VI is larger than that of NVP self-polymerization, and the polymerization degree, copolymerization ratio and monomer conversion rate of the copolymer are regulated.
In one embodiment, the free radical initiator is selected from oil soluble free radical initiators, such as azo-based free radical initiators, more specifically, the oil soluble free radical initiator has a half life of not more than 12 hours at 80 ℃, and may be selected from Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN); wherein when AIBN is selected as the free radical initiator, the temperature of the polymerization reaction is 70-80 ℃, more specifically, the temperature of the polymerization reaction is controlled to 75-78 ℃; when the free radical initiator is azodiisoheptonitrile, the polymerization reaction temperature is 55-65 ℃. AIBN is adopted as an initiator for the copolymerization of NVP and vinylimidazole, and has the advantages of uniform decomposition, generation of only one free radical and no other side reaction. In the present invention, the weight of the radical initiator may be 0.5 to 5% of the sum of the weight of the VI monomer and the NVP monomer, and further, may be 1 to 3.5%. The free radical initiator can be added into the reaction system at one time or can be added into the reaction system step by step, for example, partial free radical initiator is firstly taken and added into the reaction system together with the VI monomers, and then the rest free radical initiator is added after the VI monomers react for a period of time and before the NVP monomers are added, so that the self polymerization of the VI monomers and the copolymerization of the NVP monomers are facilitated.
Example 1:
the embodiment provides a preparation method of an N-vinyl pyrrolidone/1-vinyl imidazole copolymer, which takes water as a reaction medium of copolymerization reaction, firstly, 1-vinyl imidazole is mixed with water and then added into a reaction pot, and then initiator AIBN and NVP are sequentially added, wherein the specific operation steps are as follows:
s1, taking 0.03kg of N-vinylpyrrolidone/1-vinylimidazole copolymer (wherein the weight percentage of the polyvinylimidazole is 25%) and 30kg of deionized water in a reaction kettle, and uniformly stirring to obtain a first liquid;
s2, adding 0.022kg of AIBN into 0.2kg of VI monomer, and stirring until the AIBN is completely dissolved to obtain a second liquid;
s3, adding the second liquid into a reaction kettle containing the first liquid, stirring and mixing at the rotating speed of 600rpm to obtain a third liquid, and heating to 77 ℃ for reaction for 1 hour;
s4, 2.0kg of NVP monomer is dripped into the reaction kettle containing the third liquid at a constant speed to obtain a fourth liquid, and the reaction is continued for 3 hours to obtain a copolymer solution.
Example 2:
the difference from example 1 is that 0.6g of sodium dodecylbenzenesulfonate is also added in step S1, the remaining steps remaining unchanged.
Example 3:
the preparation process of N-vinyl pyrrolidone/1-vinyl imidazole copolymer includes the following steps:
s1, taking 0.03kg of N-vinylpyrrolidone/1-vinylimidazole copolymer (wherein the weight percentage of the polyvinylimidazole is 25%), 0.2kg of VI monomer, 0.011kg of AIBN and 30kg of deionized water, stirring and mixing uniformly at the rotating speed of 600rpm, and heating to 77 ℃ to react for 2 hours;
s2, adding 0.011kg of AIBN into the reaction solution, dripping 2.0kg of NVP monomer at a constant speed, and continuously reacting for 3 hours to obtain a copolymer solution.
Example 4:
the difference from example 3 is that 0.6g of sodium dodecylbenzenesulfonate is also added to S1, the remaining steps remaining unchanged.
Examples 5 to 8:
the difference from example 2 is that the amounts of the reaction materials added are different and the reaction steps are identical. The specific amounts of the starting materials are given in Table 1 below.
TABLE 1
Example 9:
the difference from example 6 is that the suspending agent is polyvinyl alcohol PVA17-92.
Example 10:
the difference from example 6 is that the weight percentage of polyvinylimidazole in the suspension agent is 5%.
Example 11:
the difference from example 6 is that the weight percentage of polyvinylimidazole in the suspension agent is 50%.
Comparative example 1:
this comparative example differs from example 1 in that the water was replaced with equal mass of absolute ethanol, no suspending agent was added, and the rest of the procedure remained unchanged.
In the polymerization process, the reaction system is found to be precipitated, and the precipitation is gradually increased along with the progress of the copolymerization reaction, and more precipitates are present in the product after the copolymerization reaction is finished.
Comparative example 2:
this comparative example differs from example 1 in that the water was replaced with equal mass of absolute ethanol, the rest of the steps remaining unchanged.
Precipitation is found in the polymerization process, and is gradually increased along with the progress of the copolymerization reaction, and more precipitates are formed in the product after the copolymerization reaction is finished.
Comparative example 3:
the comparative example provides a preparation method of an N-vinyl pyrrolidone/1-vinyl imidazole copolymer, and the specific operation steps are as follows:
s1, taking 0.03kg of N-vinylpyrrolidone/1-vinylimidazole copolymer (wherein the weight percentage of the polyvinylimidazole is 25%) and 30kg of deionized water in a reaction kettle, and uniformly stirring to obtain a first liquid;
s2, adding 0.022kg of AIBN into 2.0kg of NVP monomer, and stirring until the AIBN is completely dissolved to obtain a second liquid;
s3, adding the second liquid into a reaction kettle containing the first liquid, stirring and mixing at the rotating speed of 600rpm to obtain a third liquid, and heating to 77 ℃ for reaction for 1 hour;
s4, dropwise adding 0.2kg of VI monomer into the reaction kettle filled with the third liquid at a constant speed to obtain a fourth liquid, and continuing to react for 3 hours to obtain a copolymer solution.
After the obtained copolymer solution stops stirring, layering phenomenon appears, and the upper layer is an organic phase and mainly is a VI monomer through detection, which indicates that the VI monomer has incomplete reaction.
Comparative example 4:
the comparative example provides a preparation method of an N-vinyl pyrrolidone/1-vinyl imidazole copolymer, and the specific operation steps are as follows:
taking 0.03kg of N-vinylpyrrolidone/1-vinylimidazole copolymer (wherein the weight percentage of the polyvinylimidazole is 25%), 0.022kg of AIBN, 2.0kg of NVP monomer, 0.2kg of VI monomer and 30kg of deionized water, stirring and mixing uniformly at the rotating speed of 600rpm, and heating to 77 ℃ for reacting for 4 hours to obtain a copolymer solution.
And (3) test detection:
the copolymer solutions obtained in examples 1 to 11 and comparative example 4 were dehydrated and dried to obtain copolymerization products.
1. The K value of the copolymerization product was measured by a Ubbelohde viscometer, and the result is shown in Table 2 below.
2. The residual monomer content of the copolymerization product was measured by a gas chromatograph, and the results are shown in Table 2 below.
TABLE 2
| Numbering device | K value | Residual monomer content/ppm |
| Example 1 | 62 | 210 |
| Example 2 | 65 | 150 |
| Example 3 | 63 | 190 |
| Example 4 | 66 | 130 |
| Example 5 | 68 | 150 |
| Example 6 | 71 | 180 |
| Example 7 | 70 | 200 |
| Example 8 | 74 | 240 |
| Example 9 | 72 | 310 |
| Example 10 | 73 | 140 |
| Example 11 | 65 | 270 |
| Comparative example 4 | 55 | 51400 |
As can be seen from table 2, deionized water is used as a reaction medium for the polymerization reaction, vinyl imidazole exists in a system in a form of tiny droplets in a suspension manner, and NVP monomers are added into the system in a dropwise manner to perform the polymerization reaction, so that the production process of using an organic solvent as the reaction medium is replaced, the generation of flaky gelatinous substances is reduced, and a copolymerization product with high monomer conversion rate can be obtained; and the treatment of removing the organic solvent is not needed after the polymerization reaction is finished, and the process is simple.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (3)
1. A method for preparing an N-vinylpyrrolidone/1-vinylimidazole copolymer, comprising:
s1, adding a suspending agent or a mixture of the suspending agent and an auxiliary dispersing agent into water, and adding 1-vinylimidazole and AIBN under vigorous stirring;
or, adding suspending agent or a mixture of suspending agent and auxiliary dispersing agent, 1-vinyl imidazole and AIBN into water, and stirring vigorously;
the suspending agent is a copolymer of N-vinyl pyrrolidone and 1-vinyl imidazole, and the weight percentage of the polyvinyl imidazole in the suspending agent is 5-30%;
the weight of the suspending agent is 0.05-0.5% of the weight of the water;
s2, heating to a reaction temperature, reacting for a period of time, dropwise adding N-vinyl pyrrolidone, continuing to react for a period of time to obtain a copolymer solution, removing water, and drying to obtain the N-vinyl pyrrolidone/1-vinyl imidazole copolymer;
the weight ratio of the N-vinyl pyrrolidone to the 1-vinyl imidazole is 1 (0.01-0.5).
2. The method of claim 1, wherein the dispersion aid agent is present in an amount of 0.001 to 0.01% by weight of the water.
3. The process according to claim 1 or 2, wherein the sum of the weights of the N-vinylpyrrolidone and the 1-vinylimidazole is 5 to 40% by weight of the total reaction raw materials.
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